Im et al.

Nanoscale Research Letters 2012, 7:353

http://www.nanoscalereslett.com/content/7/1/353

NANO EXPRESS

Open Access

Synthesis, structure, and photovoltaic property of

a nanocrystalline 2H perovskite-type novel
sensitizer (CH3CH2NH3)PbI3
Jeong-Hyeok Im1, Jaehoon Chung2, Seung-Joo Kim2 and Nam-Gyu Park1*

Abstract
A new nanocrystalline sensitizer with the chemical formula (CH3CH2NH3)PbI3 is synthesized by reacting
ethylammonium iodide with lead iodide, and its crystal structure and photovoltaic property are investigated. X-ray
diffraction analysis confirms orthorhombic crystal phase with a = 8.7419(2) , b = 8.14745(10) , and c = 30.3096(6) ,
which can be described as 2 H perovskite structure. Ultraviolet photoelectron spectroscopy and UV-visible
spectroscopy determine the valence band position at 5.6 eV versus vacuum and the optical bandgap of ca. 2.2 eV.
A spin coating of the CH3CH2NH3I and PbI2 mixed solution on a TiO2 film yields ca. 1.8-nm-diameter (CH3CH2NH3)
PbI3 dots on the TiO2 surface. The (CH3CH2NH3)PbI3-sensitized solar cell with iodide-based redox electrolyte
demonstrates the conversion efficiency of 2.4% under AM 1.5 G one sun (100 mW/cm2) illumination.
Keywords: (CH3CH2NH3)PbI3, 2H perovskite, Dye-sensitized solar cell, Nanodot, Sensitizer

Background
Semiconductor nanocrystals have received much attention
due to quantum confinement effect, in which the continuous optical transitions between the electronic bands in the
bulk crystals become discrete in the nanocrystals and
thereby the properties of the nano-sized materials become
size-dependent [1-3]. The size-dependent optical properties
of semiconductor n anoparticles have been widely applied
in displays [4], biomedical imaging sensors [5], and photovoltaic solar cells [6]. In the case of solar cell application,
semiconductor nanomaterials can be used as a lightabsorbing material (photosensitizer) in either a solid-state
pn junction structure or a photoelectrochemical junction
type [7]. Dispersion of semiconductor nanocrystal on a
high-surface-area n-type or p-type support is an effective
method to utilize it as a photosensitizer. For this reason,
semiconductor (or quantum dot)-sensitized solar cell has
recently attracted a lot of interest [8,9]. As photosensitizers
in the semiconductor-sensitized solar cell, metal chalcogenides have been mostly studied, where Sb2S3-sensitized solar
cell demonstrated a conversion efficiency as high as 6.18%
* Correspondence: npark@skku.edu
1
School of Chemical Engineering and Department of Energy Science,
Sungkyunkwan University, Suwon 440-746, Republic of Korea
Full list of author information is available at the end of the article

at simulated one sun (100 mW/cm2) illumination [10]. Recently, a conversion efficiency of 6.54% at one sun was
reported based on perovskite semiconductor (CH3NH3)
PbI3 [11], where (CH3NH3)PbI3 was found to form in situ
on a nanocrystalline TiO2 surface from spin coating of the
CH3NH3I and PbI2 mixed solution. Moreover, an organic
inorganic hybrid perovskite structure has advantage over
other crystal structures as for the sensitizer since it has high
light absorption property and thermal stability as well. Since
the perovskite ABX3 structure was known to be stabilized
depending on the ionic radii of A and B cations in relation
with tolerance factor [12,13], it can be possible to tailor a
new perovskite-type semiconductor sensitizer by substituting methylammonium cation in the cuboctahedral A site
with longer alkyl-chain ammonium cations. Change in the
A-site cation is expected to tune the bandgap energy of
alkylammonium lead iodide perovskite sensitizer due to
change in chemical boding nature. Here, we report for the
first time on the synthesis and structural analysis of
(CH3CH2NH3)PbI3. Valence band position and optical
bandgap are evaluated by ultraviolet photoelectron spectroscopy (UPS) and UV-visible (UVvis) spectroscopy, respectively. Photovoltaic performance of a (CH3CH2NH3)
PbI3-sensitized solar cell is investigated in the presence of
an iodide-based redox electrolyte.

2012 Im et al.; Licensee Springer. This is an Open Access article distributed under the terms of the Creative Commons
Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction
in any medium, provided the original work is properly cited.

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Figure 1 Powder XRD pattern (a) and crystal structure (b) of (CH3CH2NH3)PbI3. Red and purple spheres represent Pb and I ions,
respectively.

Methods
The semiconductor sensitizer of (CH3CH2NH3)PbI3 was
prepared by direct deposition of the -butyrolactone
(Aldrich, Sigma-Aldrich Corporation, St. Louis, MO, USA)
solution with equimolar CH3CH2NH3I and PbI2 on a nanocrystalline TiO2 surface. CH3CH2NH3I was synthesized by
reacting 18.2 mL of ethylamine (2.0 M in methanol,
Aldrich) and 10 mL of hydroiodic acid (57 wt.% in water,
Aldrich) in a 250-mL round-bottomed flask at 0C for 2 h.
The precipitate was collected by evaporation at 80C for

1 h, which is followed by washing three times with diethyl

ether and then finally dried at 100C in a vacuum oven for
24 h. The synthesized CH3CH2NH3I powder was mixed
with PbI2 (Aldrich) at a 1:1 mole ratio in -butyrolactone at
80C for 2 h, which was used as a coating solution for the
in situ formation of (CH3CH2NH3)PbI3 on the TiO2 surface. The concentration of the coating solution was
42.17 wt.%, which contains 2.234 g of CH3CH2NH3I
(12.9 mmol) and 6.016 g of PbI2 (12.9 mmol) in 10 mL of
-butyrolactone.

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Table 1 Miller indices (hkl), spacing of lattice plane (d),

and XRD peak intensity (I) of (CH3CH2NH3)PbI3
hkl

dobs

dcal

Iobs

(0 0 3)

10.06

10.08

(0 0 4) (1 0 2)

7.552

7.552

100

(0 1 4) (1 1 2)

5.532

5.530

11

(1 0 6) (2 0 0)

4.357

4.360

(0 2 0)

4.057

4.060

(0 2 4) (1 2 2)

3.574

3.576

15

(0 1 8) (2 1 4)

3.422

3.424

82

(0 2 6)

3.158

3.161

(1 2 6) (2 2 0)

2.97

2.972

43

(1 0 10) (2 0 8) (3 0 2)

2.852

2.855

30

(0 2 8) (2 2 4)

2.763

2.765

48

(2 1 8)

2.691

2.693

(3 1 2)

2.548

2.693

(0 0 12) (3 0 6)

2.516

2.518

(2 2 8)

2.334

2.335

10

(1 2 11) (3 2 5)

2.199

2.201

12

(2 0 12) (4 0 0)

2.179

2.180

34

(0 2 12)

2.139

2.140

13

(3 0 10) (4 0 4)

2.093

2.095

15

(1 1 14) (3 1 10) (4 1 4)

2.028

2.028

(0 4 4) (1 4 2)

1.961

1.961

10

(3 2 10)

1.863

1.862

(0 1 16)

1.838

1.846

Table 2 Unit cell, positional, and thermal parameters for

(CH3CH2NH3)PbI3
Space group: Pmmn
a = 8.7419(2) , b = 8.14745(10) , c = 30.3096(6) , Z = 8
Rp = 15.3% Rwp = 21.0% Rexp = 9.47% 2 = 4.9
Site

B(2)a

Pb1

4e

0.75

0.5261(17)

0.1256(12)

0.66(15)

Pb2

4e

0.25

0.493(2)

0.3776(10)

0.66(15)

I1

2a

0.25

0.25

0.466(2)

3.4(2)

I2

2a

0.75

0.75

0.046(2)

3.4(2)

I3

2b

0.75

0.25

0.208(2)

3.4(2)

I4

2b

0.25

0.75

0.288(2)

3.4(2)

I5

4f

0.997(6)

0.25

0.0898(13)

3.4(2)

I6

4f

0.993(6)

0.75

0.1693(13)

3.4(2)

I7

4f

0.526(6)

0.25

0.3429(12)

3.4(2)

I8

4f

0.013(6)

0.75

0.4195(14)

3.4(2)

Structural parameters for C, N, and H atoms were not refined. aAll of the
isotropic atomic displacement parameters (B) of each atomic species were
constrained to have the same values.

Figure 2 TEM image of the (CH3CH2NH3)PbI3-deposited TiO2

nanoparticles. Arrows indicate (CH3CH2NH3)PbI3 nanodots.

Nanocrystalline TiO2 particles were prepared by hydrothermal method at 230C, and non-aqueous TiO2 paste
was prepared according to the method reported elsewhere
[14]. Fluorine-doped tin oxide (FTO) conductive glass
(TEC-8, 8 /sq, Pilkington, St Helens, UK) was pretreated with 0.1 M Ti(IV) bis(ethyl acetoacetato)-diisopropoxide (Aldrich) in 1-butanol (Aldrich) solution, in
which the nanocrystalline TiO2 paste was deposited and
heated at 550C for 1 h. The thicknesses of the annealed
TiO2 films were determined by an alpha-step IQ surface
profiler (KLA-Tencor Corporation, Milpitas, CA, USA).
The perovskite coating solution was spread on the
annealed TiO2 film (38.46 L/cm2) and was spun for 10 s
at a speed of 2,000 rpm in ambient atmosphere. The perovskite (CH3CH2NH3)PbI3 formed on the TiO2 surface
was dried at 100C for 15 min. Pt counter electrode was
prepared by spreading a droplet of 7 mM H2PtCl6xH2O in
2-propanol on a FTO substrate and heated at 400C for
20 min in air. The (CH3CH2NH3)PbI3-sensitized TiO2
working electrode and the counter electrode were sandwiched using 25-m-thick Surlyn (SX1170-25, Solaronix
SA, Aubonne, Switzerland). The redox electrolyte was
prepared by dissolving 0.9 M LiI (Aldrich), 0.45 M I2
(Aldrich), 0.5 M tert-butylpyridine(Aldrich), and 0.05 M
urea (Aldrich) in ethyl acetate (Aldrich), which was introduced into the space of the sealed electrodes prior to
measurement.
Powder X-ray diffraction (XRD) profiles were recorded
on a Rigaku D/MAX-2200/PC diffractometer (Tokyo,
Japan) using graphite-monochromated CuK radiation
( = 1.5418 ). Data were collected over the 2 range from
5 to 100 for 4 s in each 0.02 step at ambient temperature.
The TREOR software [15] was used for indexing and determining the lattice parameters. For XRD measurement,

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Figure 3 Cross-sectional SEM micrographs of (CH3CH2NH3)PbI3-deposited TiO2 film and EDS maps for titanium, lead, and iodine.

(CH3CH2NH3)PbI3 powder was obtained by drying the solution of the equimolar mixture of CH3CH2NH3I and PbI2
at 100C. Photocurrent and voltage were measured from a
solar simulator equipped with a 450-W xenon lamp
(6279NS, Newport Corporation, Irvine, CA, USA) and a
Keithley 2400 source meter (Cleveland, OH, USA). Light
intensity was adjusted with the NREL-calibrated Si solar
cell having KG-2 filter for approximating one-sun light intensity (100 mW/cm2). While measuring current and voltage, the cell was covered with a black mask having an
aperture, where the aperture area was slightly smaller than
the active area. Distribution of perovskite (CH3CH2NH3)
PbI3 in the TiO2 film was investigated by a distribution
mapping technique using an energy-dispersive X-ray spectroscope (EDS) combined with a field-emission scanning
electron microscope (FE-SEM, Jeol JSM 6700 F). X-ray energies corresponding to Ti, Pb, and I were collected as the
SEM scanned the electron beam over the surface and
cross-sectional area in the TiO2 film. The X-ray data were
synchronized with the SEM image, and an elemental mapping was created showing the presence of the selected
element throughout the selected area. Transmission electron microscope (TEM) image was investigated using highresolution TEM (HR-TEM, Jeol, JEM-2100 F) at an acceleration voltage of 200 kV. The UVvis reflectance spectra of
the powdered (CH3CH2NH3)PbI3, the (CH3CH2NH3)PbI3adsorbed TiO2 nanoparticle, and the bare TiO2 particle
were recorded using a UV/VIS/NIR spectrophotometer
(Lambda 950 model, PerkinElmer, Waltham, MA, USA) in

a wavelength of 200 to 1,100 nm. UPS equipped with He-I

source (h = 21.22 eV) (AXIS Nova, Kratos Analytical Ltd.,
Manchester, UK) was used to determine the valence band
energy of (CH3CH2NH3)PbI3.

Results and discussion

Figure 1a shows the XRD pattern of the synthesized
(CH3CH2NH3)PbI3. All reflections are indexed by an
orthorhombic unit cell with a = 8.7419(2) , b = 8.14745
(10) , c = 30.3096(6) . Reflection conditions (h + k = 2n
for hk0, h = 2n for h00, and k = 2n for 0k0) observed in the
XRD pattern indicate that possible space groups are
P21mn and Pmmn (Table 1). By assuming a centrosymmetric space group Pmmn, the structural parameters for
heavy atoms such as Pb and I are determined by applying
the direct method using the EXPO software [16] and
refined by the Rietveld method with the FULLPROF program [17]. Table 2 shows the atomic coordinates, isotropic
temperature factors, and agreement factors. The structural
information about C, N, and H atoms could not be
obtained due to the low resolution of the laboratory XRD
equipment. As shown in Figure 1b, the structure of
(CH3CH2NH3)PbI3 can be described as a 2 H perovskite
type which consists of infinite chains of face-sharing (PbI6)
octahedra running along the b-axis of the unit cell. These
chains are separated from one another by ethylammonium
ions.
Figure 2 shows TEM image of the (CH3CH2NH3)PbI3
deposited on TiO2 nanoparticles, where the (CH3CH2NH3)

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Figure 4 Diffuse reflectance spectra, UPS spectrum, and schematic energy profile for (CH3CH2NH3)PbI3. Diffuse reflectance spectra and
the transformed Kubelka-Munk function for (a, b) the bare TiO2, (c, d) the powdered (CH3CH2NH3)PbI3, and (e, f) the (CH3CH2NH3)PbI3 deposited
on TiO2. (g) UPS spectrum and (h) schematic energy profile for (CH3CH2NH3)PbI3. In UPS spectrum, binding energy was adjusted with respect to
He-I (21.22 eV).

PbI3 dots are clearly seen and sparsely distributed on the

TiO2 surface. This indicates that spin coating of the solution containing CH3CH2NH3I and PbI2 leads to
(CH3CH2NH3)PbI3 dots on the TiO2 surface. The average
size of the deposited (CH3CH2NH3)PbI3 is estimated to be
about 1.8 nm in diameter.

Figure 3 shows cross-sectional EDS mapping, where

Pb and I are well distributed three-dimensionally in the
mesoporous TiO2 film. Atomic percentages from EDS
elemental analysis are found to be 1.66% and 4.74% for
Pb and I, respectively, which indicates that the ratio of
Pb to I is close to 1:3.

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estimated to be 3.4 eV, which is 0.8 eV higher than that of

the ECB for TiO2 (4.2 eV versus vacuum).
Figure 5 shows the photovoltaic property of the
(CH3CH2NH3)PbI3-sensitized solar cell, where I3 /I
redox electrolyte is employed. A photocurrent density of
5.2 mA/cm2, a voltage of 0.660 V, and a fill factor of
0.704 are observed at AM 1.5 G one sun (100 mW/cm2)
illumination, leading to an overall conversion efficiency
of 2.4%. Incident photon-to-current conversion efficiency (IPCE) spectrum shows that the electron excitation starts to occur at around 570 nm, which is
consistent with the estimated Eg of ca. 2.2 eV.

Figure 5 Photocurrent density-voltage curve of the

(CH3CH2NH3)PbI3-sensitized solar cell under AM 1.5 G one-sun
light intensity. The 2 H perovskite-type (CH3CH2NH3)PbI3-sensitized
TiO2 layer was heated at 100C for 15 min. The active area and TiO2
film thickness were 0.323 cm2 and 5.4 m, respectively. The inset
shows the IPCE spectrum.

To determine optical bandgap and valence band position,

UVvis reflectance and UPS measurements are performed.
Figure 4a,b,c,d,e,f shows the diffuse reflectance spectra and
the transformed Kubelka-Munk spectra for the bare TiO2
nanoparticle, the powdered (CH3CH2NH3)PbI3, and the
deposited (CH3CH2NH3)PbI3 on the TiO2 surface. The dependence of the optical absorption coefficient with the photon energy has been known to help to study the type of
transition of electrons and semiconductors' bandgap energy
as well [18]. The optical absorption coefficient () can be
calculated using reflectance data according to the Kubelka2

Munk equation [19], FR 1R

2R , where R is the
reflectance data. The incident photon energy (h) and the
optical bandgap energy (Eg) are related to the transformed


1
Kubelka-Munk function, FRhp A h  Eg , where A
is the constant depending on transition probability and p is
the index that is related to the optical absorption process.
Theoretically, p equals to 2 or for an indirect or direct
allowed transition, respectively. The Eg of the bare TiO2
determined based on indirect transition is 3.1 eV, which is
well consistent with the data reported elsewhere [19]. For
the case of (CH3CH2NH3)PbI3, a transformed KubelkaMunk function can be constructed by plotting [F(R)]2
against the photon energy, which is indicative of direct
transition. As shown in Figure 4c,d,e,f, an Eg of ca. 2.2 eV is
estimated for both the powdered (CH3CH2NH3)PbI3 and
the deposited one. According to UPS spectrum, the valence
band energy (EVB) of (CH3CH2NH3)PbI3 is determined to
be 5.6 eV with respect to vacuum level. Therefore, from the
Eg and the EVB values, conduction band energy (ECB) is

Conclusions
We synthesized a new nanocrystalline sensitizer based
on organicinorganic hybridization. The crystal structure of the synthesized (CH3CH2NH3)PbI3 was determined to be 2 H perovskite-type orthorhombic phase.
The optical bandgap was estimated to be ca. 2.2 eV, and
the valence band energy position was determined to be
5.6 eV based on UPS measurement. The conduction
band edge position of (CH3CH2NH3)PbI3 was 0.8 eV
higher than that of TiO2, which allowed injection of
photo-excited electrons from (CH3CH2NH3)PbI3 to
TiO2. Under full sun illumination, the (CH3CH2NH3)
PbI3-sensitized solar cell showed an overall conversion
efficiency of 2.4%.
Competing interests
The authors declare that they have no competing interests
Authors' contributions
J-HI carried out the synthesis of perovskite materials and the fabrication of
solar cell devices. JC and S-JK carried out the X-ray diffraction measurement
and structure analysis. N-GP contributed to the conception and design of
experiments, data interpretation, and writing of the manuscript. All authors
read and approved the final manuscript.
Acknowledgements
This work was supported by the National Research Foundation of Korea
(NRF) grant funded by the Ministry of Education, Science and Technology
(MEST) of Korea under contract nos. 20110016441, 20110030359, and R312008-10029 (WCU program) and the Korea Institute of Energy Technology
Evaluation and Planning (KETEP) grant funded by the Ministry of Knowledge
Economy under contract no. 20103020010010.
Author details
1
School of Chemical Engineering and Department of Energy Science,
Sungkyunkwan University, Suwon 440-746, Republic of Korea. 2Department
of Chemistry, Division of Energy Systems Research, Ajou University, Suwon
443-749, Republic of Korea.
Received: 22 May 2012 Accepted: 17 June 2012
Published: 28 June 2012
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doi:10.1186/1556-276X-7-353
Cite this article as: Im et al.: Synthesis, structure, and photovoltaic
property of a nanocrystalline 2H perovskite-type novel sensitizer
(CH3CH2NH3)PbI3. Nanoscale Research Letters 2012 7:353.

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